Dental materials based on urethane-group-containing vinylcyclopropane derivatives

ABSTRACT

in which X, Y in each case are O or NH, wherein X and Y cannot have the same meaning, R1 is a linear or branched C1-C8-alkyl radical, which can be interrupted by O, S, an ester group or a urethane group, R2 is a linear or branched C2-C10-alkylene radical, which can be interrupted by O, S, an ester group or a urethane group, R3 is a hydrocarbon radical with 1 to 20 carbon atoms, which additionally can contain one or more N, O or S atoms, and n is 1, 2, 3 or 4, preferably 1 or 2. The vinylcyclopropanes are characterized by a low shrinkage and a high reactivity on radical polymerization and are suitable in particular for the preparation of dental materials.

TECHNICAL FIELD

The present invention relates to urethane-group-containingvinylcyclopropanes which have a high reactivity on radicalpolymerization and which are suitable in particular for the preparationof dental materials, in particular of cements, composites, coatingmaterials, bondings and adhesives. In addition, the vinylcyclopropanes are suitable for the stereolithographic production of shaped bodies.

BACKGROUND OF THE INVENTION

The polymerizable organic matrix of dental resins, cements or compositesconsists above all of a mixture of monomers, initiator components,stabilizers and pigments (J. Viohl, K. Dermann, D. Quast, S. Venz, DieChemie zahnärztlicher Füllungskunststoffe [The chemistry of dentalfilling plastics], Carl Hanser Verlag, Munich-Vienna 1986, 21-27). Asresins, mixtures of dimethacrylates are usually used (cf. A. Peutzfeldt,Resin composites in dentistry: the monomer systems, Eur. J. Oral. Sci.105 (1997) 97-116; J. W. Nicolson, H. M. Anstice, The chemistry ofmodern dental filling materials, J. Chem Ed. 76 (1999) 1497-1501; J. W.Stansburry, Curing dental resins and composites by photopolymerization,J. Esthet. Dent., 12 (2000) 300-308; N. Moszner, T. Hirt, NewPolymer-Chemical Developments in Clinical Dental Polymer Materials:Enamel-Dentin Adhesives and Restorative Composites, J. Polym. Sci. PartA: Polym. Chem. 50 (2012) 4369-4402).

A main disadvantage of the methacrylates used is that the polymerizationthereof is accompanied by a volume contraction, so-called polymerizationshrinkage. In the case of dental materials, polymerization shrinkage canlead, among other things, to disadvantageous shrinkage stresses and tomarginal gap formation in filling composites, to reduced substrateadhesion in fixing composites or coating materials and to thedimensional stability of prosthesis plastics being impaired. In thisconnection, radically polymerizable cyclic monomers have attracted greatinterest in the preparation of dental materials due to the considerablylower polymerization shrinkage compared with linear monomers, such ase.g. methacrylates (cf. R. K. Sadhir, R. M. Luck, Expanding Monomers,CRC Press, Boca Raton etc. 1992).

Vinylcyclopropanes are characterized, compared with other knownring-opening monomers such as methylene-group-containingspiroorthocarbonates (SOC), spiroorthoesters (SOE) or bicyclicorthoesters (BOE), by the fact that the vinylcyclopropyl (VCP) group isnot moisture-sensitive and in that, when it is radically polymerized,polymers with high molar masses are obtained which only containhydrolytically stable C—C bonds in the main chain (N. Moszner, F.Zeuner, T. Völkel, V. Rheinberger, Macromol. Chem. Phys. 200 (1999)2173).

From DE 198 12 888 A1, vinylcyclopropane derivatives and in particularvinylcyclopropane (meth)acrylates are known which can be copolymerizedwith acrylates and methacrylates.

Moreover, vinylcyclopropanes with several polymerizable groups areknown. F. Sanda, T. Takata, T. Endo, Macromolecules 27 (1994) 3986,describe 1-vinyl-5,7-dioxaspiro[2.5]octan-6-one, a hybrid monomer whichcontains a vinylcyclopropane group and a cyclic carbonate group, and T.Okazaki, F. Sanda, T. Endo, Macromolecules 28 (1995) 6026, describe1,10-bis(vinyl)-4,8,12,15-tetraoxatrispiro-[2.2.2.2.2.2]pentadecane, amonomer in which two vinylcyclopropane groups are joined to each othervia a hydrolysis-sensitive spiroacetal unit. These compounds do not havean improved radical copolymerizability with (meth)acrylic compounds incomparison with monofunctional vinylcyclopropanes.

EP 0 798 286 A1 relates to multifunctional vinylcyclopropane derivativeswith two to six vinylcyclopropane groups which enable the preparation ofcrosslinked polymers.

Using the example of the radical copolymerization of1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane with methyl methacrylate(MMA), it could be shown (F. Sanda, T. Takata, T. Endo, Macromolecules,(1994) 3982) that, compared with methacrylates, vinylcyclopropanes arecharacterized by a lower radical polymerizability, which considerablyrestricts their practical use. It is particularly disadvantageous thatthe known 1,1-bis(alkoxycarbonyl)-2-vinylcyclopropanes which are easy toobtain have a low photopolymerization activity.

EP 1 413 569 A1 discloses dental materials based on bicycliccyclopropane derivatives such as e.g. 2-[bicyclo[3.1.0]hex-1-yl]acrylicacid methyl ester, which exhibit an improved reactivity on radicalpolymerization (N. Moszner, F. Zeuner, U. K. Fischer, V. Rheinberger, A.de Meijere, V. Bagutski, Macromol. Rapid. Commun. 24 (2003) 269).However, these more reactive monofunctional bicyclic cyclopropylacrylates can only be obtained with great difficulty.

SUMMARY OF THE INVENTION

The object of the invention is to provide radically polymerizablemonomers which shrink only slightly on radical polymerization and whichhave a high radical polymerization reactivity, in particular onphotopolymerization. In addition, the monomers are to be easilyobtainable through synthesis and suitable for the preparation of dentalmaterials such as adhesives, cements or composites and for theproduction of coatings and shaped bodies, for example for thestereolithographic production of shaped bodies.

BRIEF DESCRIPTION OF THE DRAWINGS

Further advantages, details and features may be taken from the followingdescription of exemplary embodiments of the invention in conjunctionwith the drawings.

FIG. 1 shows graphical representations of the polymerization rate of amonomer according to the invention (VCP 1) and of a reference compound(VCP 3). The vinylcyclopropane according to the invention exhibits aconsiderably higher maximum of the polymerization rate in comparisonwith the reference compound. This shows that the compounds according tothe invention polymerize more quickly than the comparison compounds.

FIG. 2 shows graphical representations of the polymerization rate of amonomer mixture comprising a monomer according to the invention (VCP 2)and a reference compound (VCP 3) and of a mixture of two referencecompounds (VCP 4/VCP 3) The mixture VCP 2/VCP 3 is considerably morereactive than the reference mixture VCP 4/VCP 3. The results show thatthe introduction of urethane groups results in a significant increase inthe reactivity.

DETAILED DESCRIPTION

This object is achieved by urethane-group-containing vinylcyclopropanescorresponding to general formulae I:

in which

X, Y in each case are O or NH, wherein X and Y cannot have the samemeaning,

R¹ is a linear or branched C₁-C₈-alkyl radical, which can be interruptedby 0, S, an ester group and/or a urethane group,

R² is a linear or branched C₂-C₁₀-alkylene radical, which can beinterrupted by 0, S, an ester group and/or a urethane group,

R³ is a hydrocarbon radical with 1 to 20 carbon atoms, whichadditionally can contain one or more N, 0 or S atoms, and

n is 1, 2, 3 or 4, preferably 1 or 2.

The urethane group optionally present in R¹/R² is preferably anon-N-substituted group of the formula —NH—CO—O—.

Formula I and the other formulae shown herein cover all stereoisomericforms as well as mixtures of different stereoisomeric forms, such ase.g. racemates. The formulae only relate to those compounds which arecompatible with the theory of chemical valence. The indication that aradical can be interrupted by a group or a heteroatom such as O isunderstood to mean that the group or the heteroatom is inserted into thecarbon chain or the carbon ring of the radical, i.e. is bordered on bothsides by carbon atoms. The number of heteroatoms or groups is thereforesmaller by at least 1 than the number of carbon atoms, and theheteroatoms cannot be terminal. C₁ radicals cannot be interrupted. Inthe case of hydrocarbon radicals, which contain carbon atoms andheteroatoms, the number of heteroatoms is always smaller than the numberof carbon atoms without taking into account substituents. The radicalsR¹ and/or R² can be interrupted by one or more of the named atoms andgroups. Radicals are preferred which are interrupted by one group or oneatom or are particularly preferred which are not interrupted.

The vinylcyclopropanes according to the invention contain at least oneurethane group, i.e. in formula I, X must have the meaning O if Y hasthe meaning NH, or X is NH if Y represents O. X and Y cannot have thesame meaning.

The radical R³ is substituted n times by the expression in brackets. R³is a hydrocarbon radical with 1 to 20 carbon atoms, which can containone or more N, O or S atoms. Preferably R³ is an aliphatic linear orbranched C₁-C₂₀-hydrocarbon radical, which can be interrupted by O, S oran ester group, an alicyclic or aromatic C₆-C₁₄ radical or an aromaticor non-aromatic heterocyclic radical, which can contain 4 to 20 carbonatoms and 1 to 6 heteroatoms, which are selected from N, O and/or Satoms. The named cyclic radicals can be mono- or polycyclic groups. R³can also be formed by a combination of the named radicals, for exampleby a combination of one or more aliphatic and one or more aromaticgroups, e.g. an aliphatic-aromatic C₇-C₂₀ radical. Particularlypreferred are radicals which contain a tricyclodecane group (TCD).

The compounds of formula I are radically polymerizable. Compounds inwhich n is greater than 1 contain two or more vinylcyclopropane groups.Herein, such compounds are also referred to as multifunctionalvinylcyclopropanes and compounds with only one vinylcyclopropane groupare correspondingly referred to as monofunctional vinylcyclopropanes.

According to the invention, compounds of formula I are preferred inwhich the variables have the following meanings:

X, Y in each case O or NH, wherein X and Y cannot have the same meaning,

R¹ a branched or preferably linear C₁-C₄-alkyl radical,

R² a branched or preferably linear C₂-C₄-alkyl radical,

R³ an aliphatic linear or branched C₁-C₂₀-hydrocarbon radical, anaromatic C₆-C₁₄ radical, an aromatic or non-aromatic heterocyclicradical, which contains 4 to 12 carbon atoms and 1 to 2 heteroatoms,which are selected from N or O atoms, an alicyclic C₆-C₁₂-hydrocarbonradical, wherein in all cases the cyclic radicals can be mono- orpolycyclic groups, or an aliphatic-aromatic C₇-C₂₀ radical,

n 1 or 2.

According to the invention, compounds of formula I are particularlypreferred in which the variables have the following meanings:

X, Y in each case O or NH, wherein X and Y cannot have the same meaning,

R¹ a methyl or ethyl radical,

R² a linear C₂-C₄-alkylene radical,

R³ an aliphatic linear or branched C₁-C₁₀-hydrocarbon radical, anaromatic C₆-C₁₄ radical, an alicyclic C₆-C₁₂-hydrocarbon radical,wherein in all cases the cyclic radicals can be mono- or polycyclicgroups, or an aliphatic-aromatic C₇-C₁₅ radical,

n 1 or 2.

The vinylcyclopropanes of formula I are characterized by a low shrinkageand a high reactivity on radical polymerization. A subject of thepresent invention is also the use of urethane-group-containingvinylcyclopropanes of Formula I for the preparation of dental materials,in particular of dental cements, composites, coating materials, bondingsand adhesives, as well as for the preparation of materials for thestereolithographic production of molded articles. A further subject ofthe invention are molded articles, polymers and copolymers which can beobtained by homo- or copolymerization of the urethane-group-containingvinylcyclopropanes of formula I.

The urethane-group-containing monofunctional or multifunctionalvinylcyclopropanes of general formulae I can be prepared easily. Thesynthesis of 1,1-di(alkoxycarbonyl)-substituted 2-vinylcyclopropanes cantake place using known methods (cf. U.S. Pat. Nos. 4,713,478 and4,713,479) e.g. through reaction of trans-1,4-dihalogenbut-2-enes withcorresponding malonic acid esters:

For example:

2-Vinylcyclopropane-1-alkoxycarbonyl-1-carboxylic acids can be preparedfrom the 1,1-di(alkoxycarbonyl)-substituted 2-vinylcyclopropanes bypartial alkaline hydrolysis:

For example:

Corresponding hydroxyalkyl derivatives can be synthesized from the2-vinylcyclopropane-1-alkoxycarbonyl-1-carboxylic acids through reactionwith diols in the presence of dicyclohexylcarbodiimide (DCC) and4-dimethylaminopyridine (DMAP):

For example:

The reaction between such hydroxyalkyl derivatives and mono- ormultifunctional isocyanates results in the urethane-vinylcyclopropanesaccording to the invention:

For example:

Corresponding dihydroxyalkyl derivatives can be prepared from the2-vinylcyclopropane-1,1-dicarboxylic acid through reaction with diols inthe presence of DCC and DMAP. Such compounds could then react withisocyanates to form the corresponding diurethanes:

Corresponding Boc-protected amines can be synthesized from the2-vinylcyclopropane-1-alkoxycarbonyl-1-carboxylic acids through reactionwith N-Boc-hydroxyalkylamines (Boc=tert-butoxycarbonyl) in the presenceof DCC and DMAP. De-protection with trifluoroacetic acid (TFA) yieldsthe corresponding amines:

Specific example:

These amines can then be converted into urethane derivatives accordingto the invention through reaction with dialkyl carbonates.

For example:

A further possibility for the synthesis of the urethane-group-containingmono- or multifunctional vinylcyclopropanes of general formula Iconsists in the reaction of vinylcyclopropane amines with alkylchloroformates. The alkyl chloroformates can be synthesized from thebis(trichloromethyl) carbonate and the corresponding alcohol:

With this method, multifunctional vinylcyclopropanes can be prepared inthe following way:

Specific example:

Preferred examples of urethane-group-containing monofunctional ormultifunctional vinylcyclopropanes of general formulae I according tothe invention are:

The polymerizable urethane-group-containing vinylcyclopropanes ofgeneral formula I are mostly liquid and surprisingly exhibit aconsiderably improved radical polymerizability, in particular onphotopolymerization, compared with1,1-bis(alkoxycarbonyl)-2-vinylcyclopropanes, and a lower polymerizationshrinkage compared with acyclic methacrylates. Dental materials such asfixing cements or filling composites with likewise reducedpolymerization shrinkage can be prepared therewith.

The (dental) materials according to the invention preferably contain 2to 95 wt.-%, particularly preferably 5 to 85 wt.-%, quite particularlypreferably 5 to 60 wt.-% and in particular 10 to 60 wt.-%vinylcyclopropane(s) of general formula I, in each case relative to thetotal mass of the material.

In addition to one or more vinylcyclopropanes of general formula I, thematerials preferably contain at least one further radicallypolymerizable monomer. As further radically polymerizable monomers,other vinylcyclopropanes such as 1,1-di(ethoxycarbonyl)- or1,1-di(methoxycarbonyl)-2-vinylcyclopropane,bis(2-vinylcyclopropane-1-carboxylic acid ethylester-1-carbonamido)-2,2-dimethyl-4-methylhexane,1,8-bis(2-vinylcyclopropane-1-carboxylic acid ethylester-1-carbonyloxy)-3,6-dioxaoctane (VCP 5) or the esters of1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinylcyclopropane-carboxylicacid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediolor resorcinol are preferred, such as bis-(2-vinyl-1,1-dicarboxylic acidmonoethyl ester)resorcinyl ester (VCP 4), and in particular the2-vinylcyclopropanes described in N. Moszner, F. Zeuner, V. Rheinberger,Macromol. Rapid Commun. 18 (1997) 775-780, and N. Moszner, F. Zeuner, T.Volkel, U. K. Fischer, V. Rheinberger, J. Appl. Polym. Sci. 72 (1999)1775-1782. Further preferred are the bicyclic cyclopropane derivativesdisclosed in EP 1 413 569 A1, in particular2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester or thedisubstitution products in 3-position thereof such as(3,3-bis(ethoxycarbonyl)bicyclo[3.1.0]hex-1-yl)acrylic acid methyl orethyl ester.

Likewise preferred are the cyclopropyl acrylates disclosed in EP 688 125A1, in particular{3,3-bis(ethoxycarbonyl)bicyclo[3.1.0]hexa-1-yl}acrylic acid methylester and 2-(3-acetyl-3-ethoxycarbonyl-bicyclo[3.1.0]hexa-1-yl}acrylicacid methyl ester.

According to the invention, those dental materials are preferred whichcontain as comonomer at least one monofunctional vinylcyclopropane withgeneral formulae II:

in which

A, B independently of each other in each case are OH or COOH,

X, Y independently of each other in each case are O or NH,

R¹, R² independently of each other in each case are H or an aliphaticlinear or branched C₁-C₁₀-hydrocarbon radical, which can be interruptedby O, S or an ester group, an alicyclic or aromatic C₆-C₁₄ radical or anaromatic or non-aromatic heterocyclic radical, which can contain 4 to 14carbon atoms and 1 to 6 heteroatoms, which are selected from N, O and/orS atoms, and

n, m independently of each other in each case are 0, 1 or 2.

If X=Y=0, R¹≠H and R²≠H, then n+m≥1. If m=0 and R¹≠H, the free valenceat R¹ is filled by H, and if n=0 and R²≠H, the free valence at R² iscorrespondingly filled by H.

The compounds of formula II are characterized by the fact that they havegroups (CO—NH, OH, COOH) which are suitable for the formation ofhydrogen bridge bonds. The vinylcyclopropanes of formula II have a lowviscosity and are therefore particularly suitable as diluting monomersfor viscous monomers.

Compounds of formula II in which A and B have the same meaning arepreferred. Likewise, those compounds are preferred in which X and Y havethe same meaning. R¹ and R² can be identical or, preferably, different.The radicals R¹ and/or R² of formula II can be interrupted by one ormore of the named atoms and groups. Radicals are preferred which areinterrupted by one group or one atom, and particularly preferred areradicals which are not interrupted.

The named cyclic radicals of Formula II can be mono- or polycyclicgroups. R¹ and/or R² can also be formed by a combination of the namedradicals, for example by a combination of one or more aliphatic and oneor more aromatic groups, e.g. an aliphatic-aromatic C₇-C₁₄ radical.Particularly preferred are radicals which contain a tricyclodecane group(TCD).

According to the invention, compounds of Formula II are preferred inwhich the variables have the following meanings:

A OH,

m 0, 1 or 2,

R¹ H or a branched or preferably linear C₁-C₆-hydrocarbon radical, whichcan be interrupted by O, wherein radicals which are not interrupted by Oare preferred, wherein R¹ is preferably not H if X=0 and m=0,

X O or NH, wherein X is preferably NH if m=0 and R¹≠H,

n 0,

R² a branched or preferably linear C₁-C₃-alkyl radical,

Y O;

or preferably

B OH,

n 0, 1 or 2,

R² H or a branched or preferably linear C₁-C₆-hydrocarbon radical, whichcan be interrupted by O, wherein radicals which are not interrupted by Oare preferred, wherein R² is preferably not H if Y=O and n=0,

Y O or NH, wherein Y is preferably NH if n=0 and R²≠H,

m 0,

R¹ a branched or preferably linear C₁-C₃-alkyl radical,

X O.

Compounds of formula II are particularly preferred in which thevariables have the following meanings:

A OH,

m 0 or 1,

R¹ H or a linear C₁-C₆-hydrocarbon radical, wherein R¹ is preferably notH if X=0 and m=0,

X O or NH, wherein X is NH if m=0 and R¹≠H,

n 0,

R² a linear C₁-C₃-alkyl radical,

Y O;

or preferably

B OH,

n 0 or 1,

R² H or a linear C₁-C₆-hydrocarbon radical, wherein R² is preferably notH if Y=O and n=0,

Y O or NH, wherein Y is NH if n=0 and R²≠H,

m 0,

R¹ a linear C₁-C₃-alkyl radical,

X O.

In addition, the dental materials can also contain radicallypolymerizable mono- or polyfunctional (meth)acrylic acid derivatives. Bymonofunctional monomers is meant compounds with one, by multifunctionalmonomers is meant compounds with two or more, preferably 2 to 4radically polymerizable groups.

Preferred mono- or multifunctional methacrylates are methyl, ethyl,2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl(meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E),bisphenol A di(meth)acrylate, bis-GMA (an addition product ofmethacrylic acid and bisphenol A diglycidyl ether), ethoxylated orpropoxylated bisphenol A dimethacrylate, such as e.g. the bisphenol Adimethacrylate2-[4-(3-methacryloyloxyethox-yethyl)phenyl]-2-[4-(3-methacryloyloxyethyl)phenyl]propane(SR-348c) with 3 ethoxy groups or2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, UDMA (an additionproduct of 2-hydroxyethyl methacrylate (HEMA) and2,2,4-trimethylhexamethylene diisocyanate), TMX-UDMA (an additionproduct of a mixture of HEMA and hydroxypropyl methacrylate (HPMA) withα,α,α′,α′-tetramethyl-m-xylylene diisocyanate (TMXDI)), di-, tri- ortetraethylene glycol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate, as well asglycerol di- and tri-methacrylate, 1,4-butanediol di(meth)acrylate,1,10-decanediol di(meth)acrylate (D₃MA) or 1,12-dodecanedioldi(meth)acrylate.

Moreover, the dental materials can advantageously also contain radicallypolymerizable, acid-group-containing monomers, such as e.g.polymerizable carboxylic acids, phosphonic acids and phosphoric acidesters. Preferred examples of polymerizable carboxylic acid monomers aremaleic acid, 2-(hydroxymethyl)acrylic acid and4-(meth)acryloyloxyethyltrimellitic acid anhydride. Preferred examplesof suitable phosphonic acid monomers are 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethyl phosphonic acid,2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl or2,4,6-trimethyl phenyl ester. Preferred examples of suitable acidicpolymerizable phosphoric acid esters are 2-methacryloyloxypropyldihydrogen phosphate, 2-methacryloyloxyethyl dihydrogen phosphate,2-methacryloyloxyethylphenyl hydrogen phosphate,di-pentaerythritolpentamethacryloyloxy phosphate,10-methacryloyloxydecyl dihydrogen phosphate and 6-(methacrylamido)hexyldihydrogen phosphate. Acidic monomers serve primarily to improve theadhesion of the materials to dentine and/or tooth enamel. The amount ofacidic monomers preferably lies in the range of from 0 to 20 wt.-%,preferably 0 to 15 wt.-% and particularly preferably 0 to 10 wt.-%,relative to the total mass of the dental material.

Materials are particularly preferred which contain at least onemultifunctional radical monomer, i.e. a vinylcyclopropane of formula Iand/or another multifunctional radically polymerizable monomer.

The dental materials according to the invention preferably furthermorecontain an initiator for the radical polymerization. To initiate theradical photopolymerization, benzophenone, benzoin and derivativesthereof or α-diketones or derivatives thereof such as9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or4,4′-dichlorobenzil are preferred. Particularly preferably used arecamphorquinone and 2,2-dimethoxy-2-phenyl-acetophenone and quiteparticularly preferably used are α-diketones in combination with aminesas reducing agent, such as e.g. 4-(dimethylamino)benzoic acid ethylester, N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidineor triethanolamine. Particularly suitable are also Norrish type Iphotoinitiators, in particular acyl- or bisacylphosphine oxides, such asfor example the commercially available compounds2,4,6-trimethylbenzoyldiphenylphosphine oxide andbis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. Particularly suitableare also monoacyl trialkyl, diacyl dialkyl germanium, triacyl alkyl aswell as tetraacyl germanium compounds, such as e.g. benzoyl trimethylgermanium, dibenzoyl diethyl germanium or bis(4-methoxybenzoyl) diethylgermanium as well as tetrabenzoyl germanium. Mixtures of the differentphotoinitiators can also be used, such as e.g. dibenzoyl diethylgermanium in combination with camphorquinone and 4-dimethylaminobenzoicacid ethyl ester or tetrabenzoyl germanium. Advantageously, initiatorcombinations can also be used which additionally contain aromaticdiaryliodonium or triarylsulfonium salts, for example the commerciallyavailable compounds 4-octyloxyphenyl-phenyl-iodoniumhexafluoroantimonate or isopropylphenyl-methylphenyl-iodonium tetrakis(penta fluoro phenyl) borate.

As initiators for a polymerization carried out at room temperature,redox initiator combinations are preferably used, such as e.g.combinations of benzoyl peroxide with N,N-dimethyl-sym.-xylidine orN,N-dimethyl-p-toluidine. Moreover, redox systems consisting ofperoxides or hydroperoxides and reducing agents, such as e.g. ascorbicacid, barbiturates, thioureas or sulfinic acids, are also particularlysuitable. In addition, compounds of transition metals which exhibit atleast two stable valence states can be used as redox catalysts. Theseare preferably compounds of the elements copper, iron, vanadium, nickelor cobalt, wherein copper compounds are particularly preferred and theseare preferably used as compounds with good organosolubility, such ase.g. as acetylacetonate, naphthenate or 2-ethylhexanoate.

Dental materials which contain at least one photoinitiator are preferredaccording to the invention. The materials can additionally containfurther initiators.

Furthermore, the compositions used according to the invention preferablyalso contain at least one organic or particularly preferably inorganicparticulate filler, for example to improve the mechanical properties orto set the viscosity. Preferred inorganic particulate fillers areamorphous spherical materials based on oxides, such as SiO₂, ZrO₂ andTiO₂ or mixed oxides of SiO₂, ZrO₂ and/or TiO₂, nanoparticulate ormicrofine fillers, such as pyrogenic silica or precipitated silica(weight-average particle size of 10-1000 nm), as well as minifillers,such as quartz, glass ceramic or glass powder with a weight-averageparticle size of from 0.01 to 1 μm. Further preferred fillers are X-rayopaque fillers, such as ytterbium trifluoride, nanoparticulatetantalum(V) oxide, barium sulfate, mixed oxides of SiO₂ withytterbium(III) oxide or tantalum(V) oxide (weight-average particle sizeof from 10-1000 nm) and X-ray opaque glass powder, e.g. barium orstrontium aluminium silicate glasses (weight-average particle size offrom 0.2-10 μm).

To improve the bond between the filler particles and the cross-linkedpolymerization matrix, the filler particles can be surface-modified withsuitable coupling reagents. For SiO₂-based fillers such as SiO₂, quartz,glass ceramic or glass powder, trialkoxysilanes, such as e.g.3-methacryloyloxypropyltrimethoxysilane, are particularly suitable.Preferred are trialkoxysilanes which contain vinylcyclopropane groups,more preferably the vinylcyclopropane silanes described in EP 0 867 444A2, in particular 1-methoxy- or 1-ethoxycarbonyl-1-[(3-trimethoxy- or3-triethoxysilyl)propylaminocarbonyl)]-2-vinylcyclopropanes.Specifically, vinylcyclopropane silanes with the following structuresare particularly suitable:

For the surface modification of non-silicate fillers, e.g. of ZrO₂ orTiO₂, functionalized acidic phosphates, such as e.g. 10-methacryloyloxydihydrogen phosphate can also be used.

Optionally, the compositions used according to the invention can containone or more further additives, above all solvents, preferably water,ethanol or a mixture thereof, as well as stabilizers, such as e.g.polymerization stabilizers, flavouring agents, dyes, microbiocidalactive ingredients, fluoride-ion-releasing additives, opticalbrighteners, plasticizers and/or UV absorbers.

The materials according to the invention are suitable in particular asdental cements, filling materials, coating or veneering materials.

According to the invention, those dental materials are preferred whichcontain the following components:

-   -   a) 2 to 95 wt.-%, preferably 2 to 90 wt.-% and particularly        preferably 10 to 85 wt.-% of at least one vinylcyclopropane of        general formula I,    -   b) 0.01 to 5 wt.-%, preferably 0.1 to 3.0 wt.-%, particularly        preferably 0.2 to 2 wt.-% of at least one initiator for the        radical polymerization, preferably a photoinitiator,    -   c) 0 to 80 wt.-%, preferably 0 to 60 wt.-% and particularly        preferably 0 to 50 wt.-% of other monomer(s), and optionally    -   d) 0 to 85 wt.-%, preferably 0 to 80 wt.-% filler(s).

The filler content is determined decisively by the desired applicationof the dental material. Dental materials for use as coating materialparticularly preferably contain 0 to 40 wt.-%, dental materials for useas cement preferably 10-70 wt.-% and dental materials for use as fillingmaterial (filling composite) preferably 10-85 wt.-% filler(s).

Dental materials for use as filling material quite particularlypreferably have the following composition:

-   -   a) 2 to 60 wt.-%, preferably 5 to 60 wt.-% and particularly        preferably 10 to 60 wt.-% of at least one vinylcyclopropane of        general formula I,    -   b) 0.1 to 3 wt.-%, preferably 0.2 to 3.0 wt.-%, particularly        preferably 0.2 to 1 wt.-% of at least one initiator for the        radical polymerization, preferably a photoinitiator,    -   c) 0 to 50 wt.-%, preferably 0 to 40 wt.-% and particularly        preferably 0 to 30 wt.-% of other monomer(s), and    -   d) 10 to 85 wt.-%, preferably 10 to 80 wt.-% filler(s).

Unless otherwise stated, all quantities herein relate to the total massof the material. The individual quantity ranges can be chosenseparately.

Those materials are particularly preferred which consist of the namedcomponents. Furthermore, those materials are preferred in which theindividual components in each case are selected from the above-namedpreferred and particularly preferred substances.

According to the invention, those dental materials are particularlypreferred which contain exclusively monomers which have vinylcyclopropyl(VCP) groups as radically polymerizable groups.

The materials according to the invention are suitable in particular asdental materials, in particular as dental adhesives, cements, fillingcomposites and veneering materials as well as as materials for theproduction of prostheses, artificial teeth, inlays, onlays, crowns andbridges. They are characterized compared with materials based ondimethacrylates by a considerably lower polymerization shrinkage andcompared with known polymerizable cyclopropane derivatives by a betterpolymerization reactivity, in particular on photopolymerization.

The dental materials are suitable primarily for intraoral application bythe dentist for the restoration of damaged teeth (clinical materials),e.g. as dental cements, filling composites and veneering materials.However, they can also be used extraorally, for example in theproduction or repair of dental restorations, such as prostheses,artificial teeth, inlays, onlays, crowns and bridges (technicalmaterials). The materials are suitable in particular for the productionof molded articles, for example of dental restorations, by generativeprocesses, in particular by stereolithography or 3D printing (cf. A.Gebhardt, Generative Fertigungsverfahren [Generative manufacturingprocesses], 3rd ed., Carl Hanser Verlag, Munich 2007).

The invention is explained in more detail in the following withreference to embodiment examples.

EXAMPLES Example 1

Synthesis of 1-(2-ethyl carbamoyloxyethoxycarbonyl)-1-ethoxy-carbonyl-2-vinylcyclopropane (VCP-1)

Step 1: Synthesis of1-(2-hydroxyethoxycarbonyl)-1-ethoxy-carbonyl-2-vinylcyclopropane(VCP-OH)

To a stirred solution of 1-ethoxycarbonyl-2-vinylcyclopropane-carboxylicacid (36.8 g, 200 mmol), ethylene glycol (49.7 g, 800 mmol) and4-dimethylaminopyridine (DMAP, 1.22 g, 1.0 mmol) in anhydrous methylenechloride (30.0 ml), dicyclohexylcarbodiimide (DCC, 41.2 g, 200 mmol) wasadded portionwise under argon and at 0° C. Stirring continued for 30 minat 0° C. and 15 h at RT. The reaction mixture was suctioned over a fritand the residue was washed with methylene chloride (3×40 ml). Theorganic phase was washed with water (150 ml) and the aqueous phase wasextracted with DCM (2×30 ml). The combined organic phases were driedover anhydrous sodium sulfate. The solvent was distilled off undervacuum and the crude product was purified by chromatography (flashsilica gel with ethyl acetate/hexane: 1/3). 32.44 g (71% yield) of acolourless liquid was obtained as a mixture of diastereoisomers (ratio:approx. 9/1).

NMR analysis of the main isomer: ¹H NMR (400 MHz, CDCl₃): δ=1.27 (t,³J_(HH)=7.1 Hz, 3H, OCH₂ CH ₃); 1.60; (dd, ²J_(HH)=5.0 Hz, ³J_(HH)=9.0Hz, 1H, CH ₂CHCH═CH₂); 1.77; (dd, ²J_(HH)=5.0 Hz, ³J_(HH)=7.7 Hz, 1H, CH₂CHCH═CH₂); 2.62; (q, ³J_(HH)=8.5 Hz, 1H, CH₂ CHCH═CH₂); 3.82; (t,³J_(HH)=4.6 Hz, CH ₂OH); 4.14-4.29; (m, 3H, CH₂OCO); 4.38; (dt,²J_(HH)=10.7 Hz, ³J_(HH)=4.8 Hz, 1H, CH₂OCO); 5.13-5.20; (m, 1H, CH₂═CH); 5.27-5.37; (m, 1H, CH ₂═CH); 5.41-5.53; (m, 1H, CH₂═CH). ¹³C NMR(101 MHz, CDCl₃): δ=14.2 (CH₃); 20.8; (CH₂CHCH═CH₂); 31.8; (CH₂CHCH═CH₂); 35.7; (COCCO); 60.9; (CH₂OH); 61.6; (CH₂OCO); 67.1; (CH₂OCO);119.0; (CH₂═CH); 132.7; (CH₂═CH); 167.4; (C═O); 169.9; (C═O).

Step 2: Synthesis of1-(2-ethylcarbamoyloxyethoxycarbonyl)-1-ethoxy-carbonyl-2-vinylcyclopropane(VCP-1)

To a stirred solution of1-(2-hydroxyethoxycarbonyl)-1-ethoxycarbonyl-2-vinylcyclopropane(VCP-OH, 10.0 g, 43.8 mmol) and ethyl isocyanate (3.42 g, 48.2 mmol) inanhydrous methylene chloride (60.0 ml), a solution of dibutyltindilaurate (138 mg, 0.22 mmol) in anhydrous methylene chloride (10 ml)was added under argon. Stirring continued for 3 h at RT. The solvent wasdistilled off under vacuum and ethyl acetate (150 ml) was added to theresidue. The solution was washed with 5% NaOH (2×50 ml). The organicphase was dried over anhydrous sodium sulfate. The solvent was distilledoff under vacuum. 11.95 g (91% yield) of a colourless liquid wasobtained.

¹H NMR (400 MHz, CDCl₃): δ=1.14; (t, ³J_(HH)=7.2 Hz, 3H, NHCH₂ CH ₃) ;1.26; (t, ³J_(HH)=7.2 Hz, 3H, OCH₂ CH ₃); 1.59; (dd, ²J_(HH)=4.8 Hz,³J_(HH)=9.0 Hz, 1H, CH ₂CHCH═CH₂); 1.73; (dd, ²J_(HH)=4.8 Hz,³J_(HH)=7.6 Hz, 1H, CH ₂CHCH═CH₂); 2.60; (q, ³J_(HH)=8.3 Hz, 1H, CH₂CHCH═CH₂); 3.12-3.30; (m, 2H, CH ₂NH); 4.08-4.44; (m, 6H, CH₂OCO); 4.69;(s, 1H, NH); 5.11-5.17; (m, 1H, CH ₂═CH); 5.26-5.34; (m, 1H, CH ₂═CH);5.39-5.51; (m, 1H, CH₂═CH). ¹³C NMR (101 MHz, CDCl₃): δ=14.2; (CH₃);15.2; (CH₃); 20.5; (CH₂CHCH═CH₂); 31.4; (CH₂ CHCH═CH₂); 35.8; (COCCO);35.9; (CH₂NH); 61.5; (CH₂OCO); 62.2; (CH₂OCO); 63.7; (CH₂OCO); 118.7;(CH₂═CH); 132.9; (CH₂═CH); 155.9; (C═O); 167.1; (C═O); 169.4; (C═O).

Example 2 Synthesis of a TCD-diisocyanate-di-VCP-OH adduct (VCP-2)

To a stirred solution of VCP-OH (9.14 g, 40.0 mmol) and dibutyltindilaurate (166 mg, 0.26 mmol) in anhydrous methylene chloride (70.0 ml),bis(isocyanato-methyl)tricyclo[5.2.1.02′6]decane (TCD-diisocyanate(Lanxess), 5.13 g, 20.8 mmol) was added under argon. Stirring continuedfor 4 h at RT. The solution was washed with water (75 ml). The organicphase was dried over anhydrous sodium sulfate. The solvent was distilledoff under vacuum and the crude product was purified by chromatography(flash silica gel with ethyl acetate/hexane: 1/1). 11.72 g (83% yield)of a colourless resin was obtained.

¹H NMR (400 MHz, CDCl₃): δ=0.80-2.55; (m, 24H, CH, CH₂, CH ₂CHCH═CH₂,OCH₂ CH ₃); 2.60; (q, ³J_(HH)=8.3 Hz, 2H, CH₂ CHCH=CH₂); 2.88-3.14; (m,4H, CH ₂NH); 4.13-4.45; (m, 12H, CH₂OCO); 4.67-4.90; (m, 2H, NH);5.11-5.19; (m, 2H, CH ₂═CH); 5.26-5.35; (m, 2H, CH ₂═CH); 5.38-5.51; (m,2H, CH₂═CH).

Example 3 (Comparison Example) Synthesis of1,8-bis(2-vinylcyclopropane-1-carboxylic acid ethylester-1-carbonyloxy)-3,6-dioxaoctane (VCP 5)

To a stirred solution of 1-ethoxycarbonyl-2-vinylcyclopropanecarboxylicacid (12.9 g, 69.9 mmol), triethylene glycol (5.0 g, 33.3 mmol) and DMAP(81 mg, 0.67 mmol) in anhydrous methylene chloride (40.0 ml), DCC (14.4g, 69.9 mmol) was added portionwise under argon and at 0° C. Stirringcontinued for 30 min at 0° C. and 15 h at RT. The reaction mixture wassuctioned over a frit and the residue was washed with methylene chloride(3×20 ml). The organic phase was washed with HCl 1N (75 ml), a saturatedNaHCO₃ solution (75 ml) and a saturated NaCl (75 ml) solution. Theorganic phase was dried over anhydrous sodium sulfate. The solvent wasdistilled off under vacuum and the crude product was purified bychromatography (flash silica gel with ethyl acetate/heptane: 1/2). 11.6g (72% yield) of a colourless liquid was obtained.

¹H NMR (400 MHz, CDCl₃) : δ=1.26; (t, ³J_(HH)=7.2 Hz, 6H, OCH₂ CH ₃) ;1.57; (dd, ²J_(HH)═4.9 Hz, ³J_(HH)=9.0 Hz, 2H, CH ₂CHCH═CH₂); 1.71; (dd,²J_(HH)=4.9 Hz, ³J_(HH)=7.6 Hz, 2H, CH ₂CHCH═CH₂); 2.59; (q, 3J_(HH)=8.4Hz, 2H, CH₂ CHCH═CH₂); 3.62; (s, 4H, OCH ₂ CH ₂O); 3.69; (t, ³J_(HH)=4.9Hz, 4H, OCH ₂CH₂OCO); 4.12-4.35; (m, 8H, CH₂OCO); 5.10-5.16; (m, 2H, CH₂═CH); 5.25-5.33; (m, 2H, CH ₂═CH); 5.37-5.49; (m, 2H, CH₂═CH). ¹³C NMR(101 MHz, CDCl₃): δ=14.2; (CH₃); 20.6; (CH₂CHCH═CH₂); 31.4; (CH₂CHCH═CH₂); 35.8; (COCCO); 61.5; (CH₂O); 64.6; (CH₂O); 68.9; (CH₂OCO);70.6; (CH₂OCO); 118.6; (CH₂═CH); 133.0; (CH₂═CH); 167.2; (C═O); 169.6;(C═O).

Example 4 Determination of the Reactivity During Photopolymerization

The reactivity of the new monomers VCP 1 and VCP 2 was investigated incomparison with the reference compounds1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane (VCP 3) andbis-(2-vinyl-1,1-dicarboxylic acid monoethyl ester)resorcinyl ester (VCP4) respectively. To each monomer, 0.5 mol.-% bis(4-methoxybenzoyl)diethyl germanium (Ivocerin®, Ivoclar Vivadent AG) was added asinitiator and the mixture was polymerized in a Differential ScanningCalorimeter (Diamond model, Perkin Elmer) with a photopolymerizationattachment by irradiation with an LED lamp (Bluephase model, IvoclarVivadent AG) for 2 minutes at 37° C. (I=20 mW/cm²). The results arerepresented graphically in FIG. 1. The vinylcyclopropane according tothe invention VCP 1 exhibits a considerably higher maximum of thepolymerization rate in comparison with the reference compound VCP 3.

The considerably higher maximum of the polymerization rate shows thatthe VCPs according to the invention polymerize, i.e. cure, considerablymore quickly than the comparison compounds. The decisive disadvantage ofthe VCPs according to the state of the art is their slow polymerization.

The reactivity of the mixtures VCP 2/VCP 3 (1 mol/1 mol) and VCP 4/VCP 3(1 mol/1 mol) was then determined under the same conditions (0.5 mol.-%Ivocerin®, 37° C., I=20 mW/cm²). It was established that the mixture VCP2/VCP 3 is considerably more reactive than the reference mixture VCP4/VCP 3 (FIG. 2). The results prove that the introduction of urethanegroups leads to a significant increase in the reactivity.

Example 5 Preparation of Composites

Composites based on a mixture of VCP 2/VCP 5 (1/1: wt./wt.) and TCD1/TEGDMA (1/1: wt./wt.) were prepared (Table 1). The composite pasteswere prepared using kneaders. Corresponding test pieces were preparedfrom the materials which were irradiated 2 times for 3 mins with adental light source (Spectramat®, Ivoclar Vivadent AG) and thus cured.The determination of the flexural strength and flexural modulus ofelasticity was carried out in accordance with ISO standard ISO-4049(Dentistry—Polymer-based filling, restorative and luting materials)(Table 2). The measurements were carried out after 24 h storage in water(37° C.). The shrinkage was determined by buoyancy (Archimedes method)(Table 2). The composite A based on the vinylcyclopropane according toformula I has a considerably lower polymerization shrinkage than themethacrylate-based composite B.

TABLE 1 Composition of the prepared composites Composite A Composite B*⁾Component [wt.-%] [wt.-%] VCP 2 8.70 — VCP 5 8.70 — TCD 1⁷⁾ — 8.70TEGDMA¹⁾ — 8.70 Ivocerin ®⁵⁾ (initiator) 0.1 0.1 EvoCeram ® isofillerSDI⁶⁾ 34.00 34.00 Barium aluminium borosilicate glass filler²⁾ 33.5033.50 SiO₂—ZrO₂ Spherosil³⁾ 10.00 10.00 YbF₃ ⁴⁾ 5.00 5.00 *⁾Comparativeexample ¹⁾Triethylene glycol dimethacrylate ²⁾Glass powder GM 27884, 1μm, silanized (Schott) ³⁾Tokoyama Soda, ⁴⁾Auer Remy⁵⁾Bis(4-methoxybenzoyl) diethyl germanium ⁶⁾Composite filler:weight-average particle size 30-40 μm ⁷⁾

TABLE 2 Mechanical properties and volume shrinkage Flexural modulusFlexural strength of elasticity Volume shrinkage Composite (MPa) (GPa)(vol.-%) A 128.3 ± 5.0  7.8 ± 0.4 2.7 ± 0.3 B*⁾ 130.0 ± 8.9 10.2 ± 0.43.6 ± 0.5 *⁾Comparative example

Example 6 Preparation of Composites with Improved Mechanical Properties

Analogously to Example 5, the composite pastes based on VCP 4 wereprepared (Table 3). VCP 1 and VCP 3 were used as diluents. The resultsof the mechanical properties are represented in Table 4 and show thatthe highly reactive vinylcyclopropane VCP 1 leads to an improvement inthe mechanical properties in comparison with the vinylcyclopropane VCP 3which corresponds to the state of the art.

TABLE 3 Composition of the composites Composite D Composite E*⁾Component (wt.-%) (wt.-%) VCP 1 5.22 — VCP 3 — 5.22 VCP 4 12.18 12.18Ivocerin ®⁵⁾ 0.1 0.1 EvoCeram isofiller SDI⁶⁾ 34.00 34.00 Bariumaluminium borosilicate 33.50 33.50 glass filler²⁾ SiO₂—ZrO₂ Spherosil³⁾10.00 10.00 YbF₃ ⁴⁾ 5.00 5.00 *⁾Comparative example ²⁻⁶⁾as Table 1

TABLE 4 Mechanical properties of the composites Flexural modulusFlexural strength of elasticity Material (MPa) (GPa) D 108.8 ± 8.8 7.9 ±0.4 E*⁾  83.3 ± 9.1 6.3 ± 0.6 *⁾Comparative example

1. A vinylcyclopropane of general formulae I in which

X, Y in each case are O or NH, wherein X and Y cannot have the samemeaning, R¹ is a linear or branched C₁-C₈-alkyl radical, which can beinterrupted by O, S, an ester group or a urethane group, R² is a linearor branched C₂-C₁₀-alkylene radical, which can be interrupted by O, S,an ester group or a urethane group, R³ is a hydrocarbon radical with 1to 20 carbon atoms, which additionally can contain one or more N, O or Satoms, and n is 1, 2, 3 or
 4. 2. The vinylcyclopropane according toclaim 1, in which R³ is an aliphatic linear or branchedC₁-C₂₀-hydrocarbon radical, which can be interrupted by O, S or an estergroup, an alicyclic or aromatic C₆-C₁₄-radical or an aromatic ornon-aromatic heterocyclic radical, which can contain 4 to 20 carbonatoms and 1 to 6 heteroatoms, which are selected from N, O and/or Satoms, wherein the cyclic radicals can be mono- or polycyclic groups andwherein R³ can also be formed by a combination of the named radicals. 3.The vinylcyclopropane according to claim 1, in which the variables havethe following meanings: X, Y in each case O or NH, wherein X and Ycannot have the same meaning, R¹ a branched or linear C₁-C₄-alkylradical, R² a branched or linear C₂-C₄-alkyl radical, R³ an aliphaticlinear or branched C₁-C₂₀-hydrocarbon radical, an aromatic C₆-C₁₄radical, an aromatic or non-aromatic heterocyclic radical, whichcontains 4 to 12 carbon atoms and 1 to 2 heteroatoms, which are selectedfrom N or O atoms, an alicyclic C₆-C₁₂-hydrocarbon radical, wherein inall cases the cyclic radicals can be mono- or polycyclic groups, or analiphatic-aromatic C₇-C₂₀ radical, n 1 or
 2. 4. A dental material, whichcomprises at least one vinylcyclopropane according to claim
 1. 5. Thedental material according to claim 4, which additionally comprises atleast one further radically polymerizable monomer and an initiator forthe radical polymerization.
 6. The dental material according to claim 5,which comprises, as additional monomer, at least one compound, which isselected from 1,1-di(ethoxycarbonyl)- or1,1-di(methoxycarbonyl)-2-vinylcyclopropane,bis(2-vinylcyclopropane-1-carboxylic acid ethylester-1-carbonamido)-2,2-dimethyl-4-methylhexane,1,8-bis(2-vinylcyclopropane-1-carboxylic acid ethylester-1-carbonyloxy)-3,6-dioxaoctane (VCP 5), the esters of1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinylcyclopropanecarboxylicacid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediolor resorcinol, bis-(2-vinyl-1,1-dicarboxylic acid monoethylester)resorcinyl ester (VCP 4), bicyclic cyclopropane derivatives,2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester or thedisubstitution products in 3-position thereof,(3,3-bis(ethoxy-carbonyl)-bicyclo-[3.1.0]-hex-1-yl)acrylic acid methylor ethyl ester.
 7. The dental material according to claim 6, whichcontains, as additional monomer, at least one mono- or polyfunctional(meth)acrylic acid derivative, which is selected from methyl, ethyl,2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl(meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E),bisphenol A di(meth)acrylate, bis-GMA (an addition product ofmethacrylic acid and bisphenol A diglycidyl ether), ethoxylated orpropoxylated bisphenol A dimethacrylate, bisphenol A dimethacrylate2-[4-(3-methacryloyloxyethoxyethyl)phenyl]-2-[4-(3-methacryloyloxyethyl)phenyl]propane(SR-348c) with 3 ethoxy groups,2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, UDMA (an additionproduct of 2-hydroxyethyl methacrylate (HEMA) and2,2,4-trimethylhexamethylene diisocyanate), TMX-UDMA (an additionproduct of a mixture of HEMA and hydroxypropyl methacrylate (HPMA) withα,α,α′,α′-tetramethyl-m-xylylene diisocyanate (TMXDI)), di-, tri- ortetraethylene glycol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di- andtrimethacrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanedioldi(meth)acrylate (D₃MA), 1,12-dodecanediol di(meth)acrylate andacid-group-containing monomers.
 8. The dental material according toclaim 4, which additionally comprises at least one particulate filler.9. The dental material according to claim 4, which additionallycomprises at least one additive, which is selected from solvents,stabilizers, flavouring agents, dyes, microbiocidal active ingredients,fluoride-ion-releasing additives, optical brighteners, plasticizersand/or UV absorbers.
 10. Dental material according to claim 4, whichcomprises a) 2 to 95 wt.-% of at least one vinylcyclopropane of generalformula I, b) 0.01 to 5 wt.-% of at least one initiator for the radicalpolymerization, c) 0 to 80 wt.-%, of other monomer(s), and optionally d)0 to 85 wt.% filler(s), in each case relative to the total mass of thematerial.
 11. The dental material according to claim 10, which comprises0 to 40 wt.-% filler(s), for use as coating material, or which comprises10-70 wt.-% filler(s), for use as cement, or which comprises 10-85 wt.-%filler(s), for use as filling composite.
 12. The dental materialaccording to claim 11 for use as filling material, which contains a) 2to 60 wt.-% of at least one vinylcyclopropane of general formula I, b)0.1 to 3 wt.-% of at least one initiator for the radical polymerization,c) 0 to 50 wt.-% of other monomer(s), and d) 10 to 85 wt.-% filler(s),in each case relative to the total mass of the material.
 13. A method ofusing a dental material which comprises at least one vinylcyclopropaneaccording to claim 1 comprising manufacturing or repairing dentalrestorations, prostheses, artificial teeth, inlays, onlays, crowns orbridges.
 14. A method of using a dental material which comprises atleast one vinylcyclopropane according to claim 1 comprisingmanufacturing molded articles by a generative process.
 15. (canceled)16. The dental material according to claim 9, wherein the solventscomprise water, ethanol or a mixture thereof and the stabilizerscomprise polymerization stabilizers.
 17. The dental material accordingto claim 4, which comprises a) 2 to 90 wt.-% of at least onevinylcyclopropane of general formula I, b) 0.1 to 3.0 wt.-% of at leastone initiator for the radical polymerization, c) 0 to 60 wt.-% of othermonomer(s), and optionally d) 0 to 80 wt.-% filler(s), in each caserelative to the total mass of the material.
 18. The dental materialaccording to claim 4, which comprises a) 10 to 85 wt.-% of at least onevinylcyclopropane of general formula I, b) 0.2 to 2 wt.-% of at leastone initiator for the radical polymerization comprising aphotoinitiator, c) 0 to 50 wt.-% of other monomer(s), and optionally d)0 to 80 wt.-% filler(s), in each case relative to the total mass of thematerial.
 19. Dental material according to claim 11 for use as fillingmaterial, which comprises a) 5 to 60 wt.-% of at least onevinylcyclopropane of general formula I, b) 0.2 to 3.0 wt.-% of at leastone initiator for the radical polymerization which comprises aphotoinitiator, c) 0 to 40 wt.-% of other monomer(s), and d) 10 to 80wt.-% filler(s), in each case relative to the total mass of thematerial.
 20. Dental material according to claim 11 for use as fillingmaterial, which comprises a) 10 to 60 wt.-% of at least onevinylcyclopropane of general formula I, b) 0.2 to 1 wt.-% of at leastone initiator for the radical polymerization, c) 0 to 30 wt.-% of othermonomer(s), and d) 10 to 80 wt.-% filler(s), in each case relative tothe total mass of the material.